WO1997019994A1 - Compositions de resines d'oxydes de polyphenylenes - Google Patents

Compositions de resines d'oxydes de polyphenylenes Download PDF

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Publication number
WO1997019994A1
WO1997019994A1 PCT/JP1996/003488 JP9603488W WO9719994A1 WO 1997019994 A1 WO1997019994 A1 WO 1997019994A1 JP 9603488 W JP9603488 W JP 9603488W WO 9719994 A1 WO9719994 A1 WO 9719994A1
Authority
WO
WIPO (PCT)
Prior art keywords
polyphenylene oxide
oxide resin
ethylene
copolymer
acid ester
Prior art date
Application number
PCT/JP1996/003488
Other languages
English (en)
Inventor
Toru Fukada
Sadaki Yamamoto
Yasufumi Yamamoto
Original Assignee
Du Pont-Mitsui Polychemicals Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Du Pont-Mitsui Polychemicals Co., Ltd. filed Critical Du Pont-Mitsui Polychemicals Co., Ltd.
Priority to EP96939321A priority Critical patent/EP0863944B1/fr
Priority to DE69609081T priority patent/DE69609081T2/de
Priority to CA002238929A priority patent/CA2238929C/fr
Publication of WO1997019994A1 publication Critical patent/WO1997019994A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12—Polyphenylene oxides
    • C08L71/123—Polyphenylene oxides not modified by chemical after-treatment

Definitions

  • This invention relates to polyphenylene oxide resin compositions having excellent heat distortion resistance, moldability, impact resistance and resistance to chemicals.
  • Polyphenylene oxide resins are resins having excellent heat resistance, hot water resistance, dimensional stability, resistance to chemicals, mechanical properties, electrical properties and the like. However, because of their high melt viscosity, they have a poor moldability, in addition to which their impact resistance is not sufficiently large.
  • the object of the present invention is to provide polyphenylene oxide resin compositions which have various excellent properties, such as heat resistance, moldability, impact resistance, resistance to che iclas, and surface appearance.
  • a polyphenylene oxide resin composition comprising 90-99.9 parts by weight of polyphenylene oxide resin or a polymer ingredient containing polyphenylene oxide, and 0.1-10 parts by weight of an ethylene-carbon monoxide-(meth)acrylic acid ester copolymer.
  • the polyphenylene oxide used in the present invention is a polymer obtained by the oxidative polymerization of one or more phenol compounds having the general formula
  • R , R2, R3, R4 and R5 are selected from hydrogen, halogen atoms, hydrocarbon groups or substituted hydrocarbon groups, with at least one of these being a hydrogen atom) with oxygen or an oxygen-containing gas, and using an oxidative coupling catalyst.
  • Rl, R2, R3, R4 and R5 in the above general formula include hydrogen, chlorine, bromine, fluorine, iodine, methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, tert- butyl, chloroethyl, hydroxyethyl, phenylethyl, benzyl, hydroxymethyl, carboxyethyl, methoxycarbonylethyl, cyanoethyl, phenyl, chlorophenyl, methylphenyl, dimethylphenyl, ethylphenyl and allyl.
  • phenol compounds having the above general formula include phenol, o-, m- and p-cresol, 2,6-,2,5-,2,4- and 3,5- di ethylphenol, 2-methyl-6-phenylphenol, 2,6- diphenylphenol, 2 ,6-diethylphenol, 2-methyl-6- ethylphenol, 2,3,5-, 2,3,6- and 2,4,6-trimethylphenol, 3-methyl-6-t-butylpheno.l, thymol and 2-methyl-6- allylphenol.
  • the polyphenylene oxide resin is produced by the oxidative polymerization of these phenols, this may also consist of copolymerization between a phenol compound having the above general formula and a phenol compound other than those having the above-described general formula, such as a polyhydroxy aromatic compound, examples of which include bisphenol A, tetrabromobisphenol A, resorcinol, hydroquinone, and novolak resins.
  • Preferable examples that may be cited of the polymer thus obtained include homopolymers of 2,6- dimethylphenol or 2,6-diphenylphenol, and copolymers of a large amount of 2,6-xylenol and a small amount of 3- methyl-6-t-butylphenol or 2,3,6-trimethylphenol.
  • the polyphenylene oxide resin may also be obtained by the graft modification of other polymers onto the above-described homopolymer or copolymer.
  • examples that may be cited include resins obtained by the oxidative polymerization of the above-mentioned phenols in the presence of EPDM, resins obtained by the oxidative polymerization of the above-mentioned phenols in the presence of a polystyrene resin, resins obtained by the graft polymerization of styrene and/or other vinyl monomers using a radical initiator in the presence of a homopolymer or a copolymer of the above ⁇ mentioned phenols, and resins obtained by melt-kneading and reacting a homopolymer or a copolymer of the above ⁇ mentioned phenols with a polystyrene resin in the presence of a radical generator.
  • the polyphenylene oxide resin may be a resin obtained by modifying a homopolymer or copolymer of the above-mentioned phenols with a modifying agent such as a polyfunctional compound.
  • the polyphenylene oxide resin may be used together with other polymer ingredients.
  • Other polymer ingredients such as this that may be cited include polystyrene resins, polyolefins, polyesters, polycarbonates, polyamides, polyacetals, polyvinyl chlorides and synthetic rubbers. Of these, the use of polystyrene resins is especially preferable.
  • polystyrene resin here signifies a homopolymer or copolymer of a vinyl aromatic compound. More specific examples that may be cited are resins containing at least 25 wt% of styrene or a derivative thereof, such as ⁇ -Methylstyrene or vinyltoluene.
  • polystyrene resins include, as mentioned above, homopolymers of styrene or derivatives thereof, and styrene polymers modified by the mixture or interaction of natural or synthetic elastomer substances such as polybutadiene, polyisoprene, butyl rubbers, EPDM rubbers, ethylene- propylene copolymers, natural rubbers, polysulfide rubbers, polyurethane rubbers and epichlorohydrin rubbers, and styrene-containing copolymers, examples of which include styrene-based thermoplastic elastomers such as styrene-acrylonitrile copolymers (SAN), styrene-butadiene copolymers, styrene-maleic anhydride copolymers, styrene-acrylonitrile-butadiene polymers
  • SAN styrene-acrylonitrile copolymers
  • SAN styrene-
  • ABS poly- ⁇ -methyl-styrene, styrene-butadiene- styrene block copolymers and styrene-isobutylene- styrene block copolymers, or styrene-based thermoplastic elastomers obtained by the hydrogenation of the diene rubber center blocks therein.
  • Resins that are even more preferable for the present invention are polystyrene homopolymer, and rubber-modified polystyrenes obtained by polymerizing styrene in the presence of 3-30 wt%, and preferably 4-12 wt%, of polybutadiene rubber or EPDM rubber.
  • the above-described EPDM rubber is a rubbery interpolymer composed of a mixture of monoolefins and polyenes; this includes resins produced from ethylene, a-olefins and polyenes.
  • Preferable rubbery interpolymers are those which are composed of 10-90 mol% of ethylene, 10-90 mol% of a-olefins having 3-16 carbons, and 0.1-12 mol% of non-conjugated cyclic or chain-like dienes having 5-20 carbons.
  • Especially preferable types of rubbery interpolymers are those interpolymers composed of ethylene and a-olefins having 3-10 carbons, and especially propylene, non- conjugated cyclic or chain-like dienes having 5-10 carbons, examples of which include 5-ethylidene-2- norbornene, dicyclopentadiene and 1,4-hexadiene.
  • the resin employed in cases where a modified resin is used as the polyphenylene oxide resin, or where this is used together with another polymer ingredient, it is preferable for the resin employed to have a composition in which the phenol polymer or copolymer units are used in an amount of at least 15 parts by weight, preferably 15-90 parts by weight, and even more preferably 30-70 parts by weight, and the modifying ingredients or other polymer ingredients are used in an amount of no more than 85 parts by weight, preferably 10-85 parts by weight, and even more preferably 30-70 parts by weight.
  • 0.1-10 parts by weight, and preferably 0.5-5 parts by weight, of an ethylene- carbon monoxide-(meth)acrylic acid ester copolymer is blended in per 90-99.9 parts by weight of this type of polyphenylene oxide resin or, when polyphenylene oxide is used as a modified resin or is used together with other polymer ingredients, per 90-99.9 parts by weight of the combined amount of polyphenylene oxide and the other polymers.
  • (meth)acrylic acid ester means an acrylic acid ester or a methacrylic acid ester.
  • the carbon monoxide polymerization units in this copolymer are included in a ratio of 1-30 wt% and preferably 2-20 wt%, and the (meth)acrylic acid ester polymerization units are included in a ratio of 3-50 wt%, and preferably 10-40 wt%.
  • a copolymer that does not contain carbon monoxide such as an ethylene- (meth)acrylic acid ester copolymer
  • the physical properties such as the impact resistance instead decrease, and the desired improvements in the properties are not achieved.
  • the (meth)acrylic acid esters may be, for example, the approximately 1- to 10-carbon alkyl esters of acrlylic acid or methacrylic acid. Specific examples of these include methyl acrylate, ethyl acrylate, isopropyle acrylate, isobutyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, isobutyl methacrylate and n-butyl methacrylate. Of these, the use of 1- to 4-carbon alkyl esters of acrylic acid or methacrylic acid is preferable.
  • this copolymer one that has a melt flow rate, at 190°C and under a load of 2160 g, of 0.1-400 g/10 minutes, and preferably 1-100 g/10 minutes.
  • a copolymer having a melt flow rate of less than 0.1 g/10 minutes is used, the dispersion with polyphenylene oxide resin becomes inadequate and it becomes difficult to fully elicit the blending effects.
  • the melt flow rate becomes too large, there are cases in which the mechanical strength of the resin composition is compromised, which is undesirable.
  • flame-retarded thermoplastic resin compositions By blending in flame retardants in order to confer non-flammability or self-extinguish-ability to the compositions of this invention, flame-retarded thermoplastic resin compositions can be obtained.
  • Halogenated organic compounds, mixtures of halogenated organic compounds and antimony compounds, elementary phosphorus, phosphorus compounds, compounds containing phosphorus-nitrogen bonds, or mixtures of these can be used as these flame retardants.
  • resin additives that are commonly employed, in accordance with the use, in the polyphenylene oxide resin compositions of the present invention, can be suitably included.
  • plasticizers stabilizers, antioxidants, pigments, dyes, drip retardants, treatment adjuvants, inorganic mineral fillers, and fibrous, particulate, flake-like or ground glass.
  • the resin compositions of this invention can easily be prepared by a method that is itself known to the art, such as a method involving the melting or solution mixture of the thermoplastic resins. Suitable examples that may be employed include methods whereby these are fed to an extruder as pellets only, as pellets and powders, or as powders only, and are kneaded and extruded, methods whereby kneading and intimate mixture are carried out using a kneader or rollers, and the blend is extruded in the form of a sheet, and methods whereby these are mixed as solutions.
  • the starting resins used in the application examples and the comparative examples were as follows.
  • composition pellets obtained by melt kneading were injection-molded by means of an injection-molding machine at a cylinder temperature of 290°C and a mold temperature of 70-75 c C, thereby fabricating test pieces for measuring the heat distortion temperatures, Izod impact strength and tensile strength.
  • Izod Impact Strength A V-notch was made in melt-molded test pieces having a thickness of 3.2 mm, and the Izod impact strength was measured in general accordance with ASTM D256.
  • composition (parts by weight) Modified polyphenyl oxide resin 99 98 97 95 98 97 100 95 97
  • the melt viscosity of a modified polyphenylene oxide resin can be lowered without lowering the heat distortion temperature of the same resin, thereby enhancing the moldability, and also giving a composition having an enhanced impact resistance.
  • compositions of the present invention blend in a larger amount of ethylene copolymer as a modifier than compositions obtained by the formulation of ethylene- unsaturated carboxylic acid ester copolymers, given that a decreasing trend in the Izod impact strength is not apparent, large amount of ethylene copolymer can be formulated. This is also excellent with respect to the peeling effect in the molded articles.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne une composition de résine d'oxyde de polyphénylène dont la formulation pondérale comporte 90 à 99,9 parties de résine d'oxyde de polyphénylène ou d'un composant polymère incluant de la résine d'oxyde de polyphénylène pour 0,1 à 10 parties de copolymère d'un ester d'acide monoxyde-(méth)acrylique d'éthylène-carbone. De telles compositions conviennent particulièrement comme plastiques industriels à haut rendement. Ces compositions, qui sont caractérisées par une malléabilité accrue et une résistance accrue au choc des résines d'oxyde de polyphénylène, admettent l'adjonction de grandes quantités de copolymères d'éthylène comme modificateurs, sans amoindrir les propriétés physiques, et présentent diverses caractéristiques intéressantes telles que la résistance à la chaleur, la malléabilité, la résistance au choc, la résistance à l'agression chimique et une surface de bel aspect.
PCT/JP1996/003488 1995-11-29 1996-11-28 Compositions de resines d'oxydes de polyphenylenes WO1997019994A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP96939321A EP0863944B1 (fr) 1995-11-29 1996-11-28 Compositions de resines d'oxydes de polyphenylenes
DE69609081T DE69609081T2 (de) 1995-11-29 1996-11-28 Zusammensetzungen aus polyphenylenethern
CA002238929A CA2238929C (fr) 1995-11-29 1996-11-28 Compositions de resines d'oxydes de polyphenylenes

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP31024995A JP3660035B2 (ja) 1995-11-29 1995-11-29 ポリフェニレンオキシド樹脂組成物
JP7/310249 1995-11-29

Publications (1)

Publication Number Publication Date
WO1997019994A1 true WO1997019994A1 (fr) 1997-06-05

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP1996/003488 WO1997019994A1 (fr) 1995-11-29 1996-11-28 Compositions de resines d'oxydes de polyphenylenes

Country Status (4)

Country Link
EP (1) EP0863944B1 (fr)
JP (1) JP3660035B2 (fr)
DE (1) DE69609081T2 (fr)
WO (1) WO1997019994A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2850662A1 (fr) * 2003-02-04 2004-08-06 Atofina Procede pour ameliorer la productivite de la fabrication d'articles a base de polymeres thermoplastiques et articles ainsi obtenus

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4084515A (en) * 1976-09-16 1978-04-18 Pullman Incorporated Locking mechanism for hopper door actuator assembly
US4526927A (en) * 1982-07-15 1985-07-02 Basf Aktiengesellschaft Thermoplastic molding materials
EP0308743A1 (fr) * 1987-09-18 1989-03-29 BASF Aktiengesellschaft Masses à mouler thermoplastiques à base de polymères de styrène et de poly(éthers de phénylène)
WO1989004346A1 (fr) * 1987-11-13 1989-05-18 E.I. Du Pont De Nemours And Company Composition thermoplastique flexible
EP0448749A1 (fr) * 1988-08-25 1991-10-02 E.I. Du Pont De Nemours And Company Mélanges thermoplastiques contenant un terpolymère de l'éthylène et son procédé de préparation
EP0488119A2 (fr) * 1990-11-26 1992-06-03 Nippon Petrochemicals Company, Limited Composition moulable de résines thermoplastiques

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4084515A (en) * 1976-09-16 1978-04-18 Pullman Incorporated Locking mechanism for hopper door actuator assembly
US4526927A (en) * 1982-07-15 1985-07-02 Basf Aktiengesellschaft Thermoplastic molding materials
EP0308743A1 (fr) * 1987-09-18 1989-03-29 BASF Aktiengesellschaft Masses à mouler thermoplastiques à base de polymères de styrène et de poly(éthers de phénylène)
WO1989004346A1 (fr) * 1987-11-13 1989-05-18 E.I. Du Pont De Nemours And Company Composition thermoplastique flexible
EP0448749A1 (fr) * 1988-08-25 1991-10-02 E.I. Du Pont De Nemours And Company Mélanges thermoplastiques contenant un terpolymère de l'éthylène et son procédé de préparation
EP0488119A2 (fr) * 1990-11-26 1992-06-03 Nippon Petrochemicals Company, Limited Composition moulable de résines thermoplastiques

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2850662A1 (fr) * 2003-02-04 2004-08-06 Atofina Procede pour ameliorer la productivite de la fabrication d'articles a base de polymeres thermoplastiques et articles ainsi obtenus
EP1445286A1 (fr) * 2003-02-04 2004-08-11 Atofina Procédé pour améliorer la productivité de la fabrication d'articles à base de polymères thermoplastiques et articles ainsi obtenus

Also Published As

Publication number Publication date
JPH09151314A (ja) 1997-06-10
JP3660035B2 (ja) 2005-06-15
EP0863944A1 (fr) 1998-09-16
EP0863944B1 (fr) 2000-06-28
DE69609081D1 (de) 2000-08-03
DE69609081T2 (de) 2000-11-02

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